N-hydroxy-amino-s-triazines

ABSTRACT

Substituted hydroxylamines exhibit activity as anti-oxidants for a diverse group of substrate materials under specific conditions of exposure to an oxidizing environment. Illustrative embodiments of substituted hydroxylamine anti-oxidants are bis(pnitrobenzyl)hydroxylamine and 2-diethylamino-4,6,-bis(N-n-propylN-hydroxyamino)-s-triazine.

United States Patent [191 Klemchuk June 18, 1974N-HYDROXY-AMINO-S-TRIAZINES [76] Inventor: Peter Klemchuk, 14s UplandRd., [561 References CM Yorktown Heights, NY. 10598 UNITED STATES ATENTS3,364,215 1/1968 Hackmann el! al 260/249.8 [22] 1972 3,505,326 4/1970Shaw 260/2498 [21] Appl. No.: 296,448

Related US. Application Data Ford [62] gvilscigxilegf Ser. No. 133,700,April 13, 1971, [57 ABSTRACT a Substituted hydroxylamines exhibitactivity as anti- [52] Us Cl 260/249 5 260/249 8 260/249 6 oxidants fora diverse group of substrate materials 8 N 6 5 6 24 under specificconditions of exposure to an oxidizing 99/16'3 44/63 6 4 R 266/293environment. Illustrative embodiments of substituted 260/247 7 A 260/293260/513' hydroxylamine anti-oxidants are bis(p-nitrobenzyl)hy- 260/561droxylamine and 2-dietl1ylamino-4,6,-bis(N-n-propyl- 51 Int. Cl. C07d55/18, C07d 55/20 N'hydmxyamm)s'trlazme- [58] Field of Search 260/2498 2Claims, No Drawings N-HYDROXY-AMINO-S-TRIAZINES This is a division ofapplication Ser. No. 133,700, filed on Apr. 13, 1971, now abandoned.

The present invention relates to substituted hydroxylamines and moreparticularly to a process for stabilizing a vast and diverse group oforganic materials against oxidation; that is against deterioration inthe presence of air, oxygen or ozone, and to stabilized compositionscontaining said substituted hydroxylamines.

The prevention of oxidation of various organic materials is obviously ofprimary industrial concern and therefore anti-oxidants are used in oradded to a wide variety of commercial products such as rubber products,oils, plastics, organometallic products, foods, etc., which are normallysubject to oxidative deterioration.

One group of hydroxylamine anti-oxidants of the present invention isrepresented by the formula wherein R R and R are alkyl, dialkyl amino,monoalkyl amino, hydroxylamino, alkyl hydroxylamino, alkylthio, alkoxy,phenoxy or alkyl phenoxy, the alkyl and alkoxy groups containing from 1to 12 carbon atoms, with the proviso that at least one of R,, R and R isa hydroxylamine or alkyl hydroxylamino group.

Another group of compounds is represented by the formula R,[ cHi nyJ-X]mwherein R is HON, HONH or HONR wherein R is alkyl or phenylalkyl, thealkyl groups containing from 1 to 3 carbon atoms, In and n are theintegers l or 2, X is amino, mono alkylamino, di-alkylamino or alkoxy,the alkyl and alkoxy groups containing from 1 to 12 carbon atoms.

A further group of compounds of the present invention is represented bythe formula [RalTKCI-h) 11303] M wherein R is alkyl or phenylalkyl, thealkyl groups containing from 1 to 3 carbon atoms, n is an integer from 1to 4, m is an integer from 1 to 3 and M is a metal cation such as analkali metal or alkaline earth metal- Still another group of compoundsof the present invention is represented by the formula N OHchloro-s-triazine is reacted with hydroxylamine or alkyl hydroxylamine.An alternative procedure involves the reaction of a benzyl halide withhydroxylamine or alkyl hydroxylamine. Another procedure involvesreaction of a di-substituted amine that is, a di-alkylamine. with methylacrylate to form a tertiary amine which is then oxidized as, forexample, with peracetic acid and the resulting amine oxide is thentreated with alkali such as sodium hydroxide, ammonium hydroxide, sodiumcarbonate and the like, to form the desired hydroxylamine product. Stillanother procedure involves the reaction of hydroxylamine or mono-alkylhydroxylamine with an acrylic acid ester or amide such as, for example.ethyl acrylate. lauryl acrylate or acrylamide.

A further procedure for preparing novel hydroxylamines of the presentinvention involves reacting a monoalkyl hydroxylamine with a sultone,i.e., a cyclic sulfonate ester.

It has been found that the substituted hydroxylamine compounds of thepresent invention are excellent antioxidants and consequently, onincorporating such substances into various organic substances whichundergo oxidative deterioration in the presence of air, oxygen or ozone,there is a surprising and unexpected inhibition of said oxidativedeterioration.

Thus'the compounds of this invention are useful as anti-oxidants in awide variety of oxygen sensitive materials. For example, liquidhydrocarbon fuels such as, kerosine fuel oil, etc. are characterized byincreased storage stability by including therein one or more of theoxidants of the present invention. It has been found that liquidhydrocarbon fuels such as gasoline which contain organometallicadditives such as tetraethyl lead as well as other organometalliccompounds which are used as fuel additives exhibit increased oxidativestability by use of the compounds of the present invention. This is alsotrue of lubricating oils and functional fluids derived from naturallyoccurring hydrocarbons such as turbine, hydraulic, transformer and otherhighly refined industrial oils; soaps and greases; plastic materials;synthetic polymers such as polyethylene and polypropylene, etc. Theaddition of small amounts of the compounds of the present invention tothe aforesaid materials greatly increase their resistance todeterioration in the presence of air, oxygen or ozone. Furthermore, suchfuels which contain halogen and phosphorus-containing scavengers for theorganometallic compounds referred to above are also stabilized by theantioxidants of the present invention.

It should also be mentioned that the compounds of the present inventionare also valuable in protecting paraffin and micro-crystalline petroleumwaxes against the oxidative deterioration which leads to rancidity.Furthermore, the compounds of this invention are extremely useful in thestabilization of fats and oils of animal or vegetable origin whichbecome rancid during periods of storage due to oxidative deterioration.Typical fats and oils include butter fat, lard, beef tallow, fish oilssuch as cod liver oil, as well as various foods containing or preparedin animal fats which tend to deteriorate, i.e., potato chips, friedfish, donuts, crackers and various types of pastry as well as cakes andcookies. Still further, fat fortified animal feeds and fish meals usedas animal feeds are not only protected against oxidative deteriorationby the use of the hydroxylamine compounds of the present invention butin addition, the aforesaid compounds inhibit the degradation of vitaminsA, D and E and certain of the B complex vitamins. The compounds of thepresent invention are also advantageously helpful in compositionscontaining oils derived from vegetable sources such as castor oil,soybean oil, rapeseed oil, coconut oil, olive oil, palm oil, corn oil,sesame oil, peanut oil, babassus oil, citrus oil and cottonseed oils aswell as compositions containing these oils such as peanut butter,peanuts and other whole nuts, salad dressings, margarine and othervegetable shortenings.

Specific hydroxylamines which are useful as antioxidants include, forexample, N,N-dibenzyl hydroxylamine,2-diethylamino-4,6-bis-(N-methyl-N-hydroxyamino)-s-triazine of theformula T ia s;

2,4-bis(N-hydroxyamino)-6-diethylamino-s-triazine of the formulaITITEJEQT I/ N EN Him NH 0 H 2,4-bis(dibutylamino)-6-N-hydroxyamino-striazine of the formula Bis-( 3 ,5-di-t-butyl-4 hydroxybenzyl)hydroxylamine of the formula2-Octylthio-4,6-bis-N-(hydroxyamino)-s-triazine of the formula star 117"N HNOHkN HNOH N-hydroxy 2,2,6,6-tetramethyl-4-piperidone of the formulamo on;

2 4-bis-( octylthio) G-N-hydroiiyamino-s-triazine of the formula IP'HOHA a 11 k J- a 11 N Bis-(p nitrobenzyl)hydroxylamine of the formula(OrlNQOHz) NOH 2,4- Bis-(dodecylamino)-6-N-hydroxyamino-striazine of theformula NHOH I A C12H25N-k LN C 121125 I N l H H N -HNOH HNOH Sodium3-(N-n-propyl-N-hydroxyamino)propane sulfonate of the formula M6Eizhlff6fifi Bis-(Z-chlorobenzyl hydroxylaniino of the formula lii-i'zchibr'obhz ij hydroxylamine of the formula $1 2Iodecylamino-4,6-bis-(N-n-prOpyI-N hydrOX- yamino)-s-triazine of theformula NOH N C HflII -kN/ ITI C 3H1 OH OH Bis- 216-dichlorobenzyl)hydroxylarnine of the formula Goa, NOH

c1 1 Bis-(3,4-dichlorobenzyl) hydroxylamine of the formula NOH orcn= NOH2-Diethylamino-4,6-bis-(N-n-propyl-N-hydroxyamino)-s-triazine of theformula N-propyl-N-(p-chlorobenzyl) hydroxylamine of the fonnyla V V ciorm oan1 WMMMMMWW 77; OHZ-(N-n-propylhydroxyamino)-4,6-bis-(diethylarnino)-s-triaz ine of theformula I]I(C2Hs)2 0 HO N[CH:C z NKJHah]:

TABLE I Performance in Tetralin Oxygen Uptake Test (60C. 2.50 MTetralin, 2.0 X l0 M anti-oxidant 3.0 X IO M azo bis isobutyronitrile,Chlorobenzene solution) Initial Slope (X 10*) mIJmin. 30.0 0.12 0.13

Induction Anti-oxidant Period None I29 I l l NONEN,N-Dibenzylhydroxylamine 2-Diethylamino-4,6-bis-(Nmethyl-N-hydroxyamine)-s-triazine 2,4-Bis-(dibutylamino)-6-N hydroxyamino-s-triazine Bis-( 3,5-di-t-butyl-4-hydroxybenzyl)hydroxylamine MonobenzylhydroxylamineN-hydroxypiperidine TABLE I-Continued Performance in Tetralin OxygenUptake Test (60C. 2.50 M Tetralin.

2.0 X H) M antioxidant 3.0 X l0" M azo bis isobutyronitrile.Chlorobenzene solution) Initial Induction Anti-oxidant Slope Period Bis(p-nitrobenzy[)hydroxylamine 0.00 l N-hydroxymorpholine 0. 38 l 7 5 Bis-(4-chlorobenzyl)hydroxylamine 0.62 l 68 Bis-(Z-chlorobenzyl)hydroxylamine 0.34 l5? Bis-(2,6-dichlorobenzyl)hydroxyl-0.36 189 amine 2-Diethylamino-4,6-bis-( N-npropyl-N-hydroxyamino-s- 0.25166 triazine FIG. 1 below shows a typical plot of oxygen uptake versustime for an inhibited tetralin oxidation. The induction period sloperepresents a measure of the radical trapping ability of theanti-oxidant; the lower the slope, the more efficient is the radicaltrapping. It is noted that there is a dramatic increase in radicaltrapping ability when anti-oxidants are added.

FIG. 1

Plot of Oxygen Uptake vs Time for Hydroxylamine Antioxidant Vol. 0

b time a. Initial Slope b. Induction Period c. Post-induction Slope d.Uninhibited Oxidation The length of the induction period is a matter ofstoichiometry, usually two radicals being trapped per antioxidantmolecule. However, deviations from this 2:1 ratio are frequentlyobserved, due, presumably, to inhibitor instability or to chemistrywhich is different from the usual. During the post induction period, therate of oxygen uptake should be the same as that for uninhibitedtetralin oxidation, but this is not always the case and the reasons fordeviations are not known.

Hydroxylamine anti-oxidants have been tested in a variety ofrepresentative substrate materials as set out in the following tables.For example, the hydroxylamine anti-oxidants perform well in cyclohexeneat C (Table II), in lard at 100 C (Table III) and are also operative inmineral oil (Table IV) and ABS resin at 300 F (Table V). The testsgiven. in Table VI show that the subject hydroxylamines exhibit aremarkable light stabilization when incorporated in polypropylene.

TABLE II Anti-oxidant Performance in Cyclohexene. l00C InductionN-hydroxymorpholinc I 3 l 2-Diethylamino-4.6-bis-(N-methyl-N-hydroxyamino)-s-lriazinc 148 TABLE VI 2,4-Bis-(dibutylamino)-6-NJrydroxyamino-s-lriazine 2-Diethylamino-4,6-bis-(N-n-propyl-N-hydroxyamino-s-triazine l 83Bis-(p-nitrobenzyl)hydroxylamine 2,4-Bis-(dodecylaminol-6-N-hydroxyamino-s-triazine I I0 TABLE III Performance ofHydroxylamine Anti-oxidants in Lard; 100. 0.05% Anti-oxidant inductionAntioxidant Period Hours None 4 N,Ndibenzylhydroxylamine 482'Diethylamino-4,6-bis-(N-methyl-N-hydroxyamino)-s-triazine 322,4-Bis-(dibutylamino)-6-N-hydroxyamino-s-triazine Bis-( 3.5-di-t-butyl-4-hydroxybenzyl) 75 hydroxylamine TABLE IV erformance ofHydroxylamine Anti-oxidants in Mineral Oil, 150C,

0.1% anti-oxidant Induction Anti-oxidant Period Hours None 2.3

2-Diethylamino-4,6-bis-( N-methyl-N-hydroxyamino)-s-triazine 422,4-bis-( dibutylamino)-6-N-hydroxyamino-s triazine TABLE Vl-lydroxylamines Performance of Hydroxylamine Anti-oxidants inPolypropylene 0.5% Anti-oxidant Anti-oxidants incorporated by MillingAnti-oxidant Fadeometcr Failure Time (hrs) None 1002-Diethylamino-4.6-bis- (N-methyl-N-hydroxyamino )-s- 900 0 triazine2,4-Bis-dibutylaminol-6-N hydroxyamino-s'triazine 700 Anti-oxidantsIncorporated by Powder Pressing None 60 2-Diethylamino-4.6-bis-(N-methyl-N-hydroxyaminol-s- 780 triazine 2-Octylthio-4,6-bis-(N-hydroxyamino)-striazine 280 2,4-Bis-(octylthio)-6-N-hydroxyamino-s-triazinc 480 2.4-Bis-(dodccylamino)-6-N-hydroxyamino-s-lriuzine 660 The following examples illustrate theprocedures used for the production of the subject substitutedhydroxylamines. The temperatures therein are given in degreescentigrade.

EXAMPLE 1 2-Octylthio-4,6-bis-(N-hydroxyamino)-s-triazine Hydroxylaminehydrochloride (117.3 g, 1.69 mole) was dissolved in water and to thissolution there was added 62.5 g (1.56 moles) of a sodium hydroxidesolution, the addition being effected dropwise at a temperature of lessthan 22. 2-Octylthio-4,6-di-chloro-striazine (60 g, 0.186 moles) in 180ml of dioxane was added to this solution, the addition being effected ina thin stream for a period of about 10 minutes at a temperature lessthan 15. A gummy solid separated after a period of stirring. The mixturewas warmed to a temperature of between 55 and 60, and stirred at that 40temperature for 1 hour. The mixture was then heated Performance in ABSResin, 300F Carbonyl Values/mil at times indicated at reflux for 3 hoursand then poured into a liter of water after cooling. There was obtaineda gummy precipitate. The solution was decanted and the solid wasdissolved in ether. The phases were separated and the decanted solutionwas extracted with ether. The ethereal solutions were combined andwashed with water. The ethereal solution was concentrated first at atmo-Compound Initial 30 min. min. min. min. min.

0.1% inhibitor None .060 .128 0.22 a a a 2-Diethylamino-4,6-bis-(N-methyl-N-hydroxyamino)- .044 .041 .042 .048 .054 0.089

s-triazine 2,4-bis-(dibutylarnino)-6- N-hydroxyamino-s-triazine .047.080 .13 .20 a a 0.1% Inhibitor, 5.0% Titanox AMO None .048 .105 .19 .21a a 2-Diethylamino-4,6-

bis-(N-methyl-N-hydroxy .044 .044 .047 .055 .080 0.12

amino)-s-triazine 2,4-Bis-(dibutylamino)-6- .043 .099 0.15 .20 a a N-hydroxyamino-s-triazine "too high to measure accurately fanntase titaniumdioxide Analysis for C H Ns z Calcd.: C. 45.97; H. 7.37: N. 24.37 Found1 C, 45.73; H, 7.16; N. 24.16

EXAMPLE 2 2,4-Bis-(octylthio)-6-N-hydroxyamino-s-triazine The procedureset out in Example 1 above was followed except that 58.6 g (0.845 moles)of hydroxylamine hydrochloride and2,4-bis-(octylthio)-6-chloro-striazine were used. The reactionwascarried out and at the end of the reaction period, the product wascooled and allowed to stand overnight. Two liquid phases were present.The upper organic phase solidified. The reaction product was poured into1 liter of water, filtered and washed with water. This was followed bydrying under vacuum and there was obtained a yield of 72 g of productwith a melting point of 87-90. On recrystallization from ethanol, therewas obtained 54.7 g of a product was a melting point of 9 l .5-92.5. Theproduct was recrystallized from ethanol'with a charcoal treatment.Product recovery 45.4 g; m.p. 92.593.5.

Analysis for C H ,;N,OS

Calcd.: C, 56.9; H, 9.06: N, 13.99 Found C, 57.32; H, 9.06; N, 14.09 C,57.34; H, 9.08; N, 14.03

EXAMPLE 3 Bis( p-nitrobenzyl hydroxylamine) Hydroxylamine hydrochloride(31.5 g; 0.45 mole) was dissolved in 75 mililiters of water and thesolution was then cooled to a temperature of Sodium hydroxide (18.6 g,0.45 mole) in 75 mls. water was then added at a temperature of 05. Asolution of 51.5 g of 4-nitrobenzyl chloride (0.3 mole) in 500 mls. wasadded and the mixture was then heated to reflux for four hours. Thesewas some precipitate formed which was filtered off while hot. Thesolution was then cooled and the product filtered and washed with water.The product weighed about 23 g (slightly moist). On recrystallizationfrom methyl cellosolve/water, yellow crystals were obtained 18.4 gmelting between 159 and 161.

Analysis for C H N O Calcd.: C, 55.44; H. 4.32; N, 13.86 Found 1 C,55.17; H, 4.36; N. 13.93

EXAMPLE 4 Didodecyl B,Bhydroxyiminodipropionate Hydroxylaminehydrochloride (4.0 g) was dissolved in 100 mls. of methanol and theresulting solution was added, at a temperature of 10 to 2.7 g of sodiummethoxide in 50 mls. methanol. A solution of 24.0 g oflauryl acrylate in100 mls. of methanol was added at 5 and the temperature was allowed torise slowly. At the reaction was noticeably strongly exothermic andneeded cooling. At the same time, the reaction mixture thickened andmls. of ether was added to keep it Analysis for C H NO Calccl: C. 70.13;H. 11.58; N, 2.7

3 Found C. 70.00; H, 11.50; N, 2.68

EXAMPLE 5 2-Dodecylamino-4,6-bis-(N-n-propyl-N-hydroxyamino)-s-triazineA solution of 1 mole of dodecylaamine in dioxane was added in abouttwenty minutes at a temperature of less than 25, maintained with icebath cooling, to a thin slurry of cyanuric chloride in dioxane/ water.An aqueous solution of 1 mole of sodium hydroxide was added theretorapidly at a temperature of less than 40 and the reaction mixture wasthen poured into a liter of water. A light tan gummy solid solidifiedwhich was filtered, washed with water and dried under vacuum to constantweight. A yield of 157.0 g (94.5 percent) of product was obtained with amelting point of 63-65. The product2-dodecylamino-4,6-dichloro-s-triazine, was recrystallized fromn-heptane and was obtained in the form of a colorless amorphous productmelting between 64.0 and 650.

A dioxane solution of 15.8 g (0.21 mole) of n-propyl hydroxylamine in adioxane solution was added to a slurry of 33.3 grams (0.10 mole) of2-dodecylamino- 4,6-dichloro-s-triazine in dioxane over a 30 minuteperiod at a temperature of less than 5. A sodium hydroxide solution wasadded at a temperature of less than 5 until the reaction mixture wasslightly alkaline to phenolphthalein. The solution was warmed at atemperature between 45 and 50 for one hour at the end of which time theremainder of sodium hydroxide solution was added to make a total of 0.20mole. The reaction product was filtered at 20 to remove a small amountof colorless solid. The light purple filtrate was added to about 1,500mls. of ice cold water. A gummy precipitate was obtained and thematerial was decanted, washed with water and dried under vacuum. Theyield of tacky purple solid was 35.0 g (85.4 percent). The product wasrecrystallized twice from n-heptane and there was obtained the desiredproduct melting between 9l.5 and 930.

Analysis for C H N O Calc'd.: C, 61.43; H. 10.31; N, 20.47 Found C,61.33; H. 10.24; N, 20.48

EXAMPLE 6 2-Dodecylamino-4,6bis-(N-hydroxyamino)-s-triazine2-Dodecylamino-4,6-dichloro-s-triazine was prepared, using the proccduredescribed in Example 5 above.

A solution of free hydroxylamine was prepared under nitrogen by theaddition, at a temperature of less than 22 of an aqueous solution of1.46 moles of sodium hydroxide to a concentrated aqueous solution of1.60 moles of hydroxylamine hydrochloride. A hot dioxane solution of66.6 g (0.20 moles) of 2-dodecylamino-4,6

Calc'd.: c. 55.19; H, 9.36; N. 25.15 Found C, 55.62; H, 9.44; N, 25.53

EXAMPLE 7 2,4-Bis-(dodecylarnino)-6N-hydroxyamino-s-triazine2,4-Bis-(dodecylarnino)6-chloro-s-triazine was prepared following theprocedure described in Examples 5 and 6 above for the preparation of2-dodecylamino- 4,6-dichloro-s-triazine except that 2 moles of the aminewere used with 1 mole of cyanuric chloride. The reaction withhydroxylamine was carried out as described, using the procedure ofExample 6 above, except that the following quantities of materials wereused: 0.37 mole of sodium hydroxide, 0.40 mole of hydroxylaminehydrochloride, 0.10 mole of s-triazine derivative. The crude product wasobtained in a 41.2 g yield (86.3 percent with a melting point of 125l27. On recrystallization, twice from dioxane, the desired produce wasobtained, possessing a melting point of 124l25.5.

Analysis for C H N O Calcd.: C, 67.73; H, 11.37; N, 17.56 Found C,67.79; H, 11.10; N, 17.67

EXAMPLE 8 from n-heptane, the melting point was found to be be-- tween76.5 and 785.

To a solution of 15.0 g (0.20 mole) of n-propylhydroxylamine in 60millimeters of 1:1 dioxane/water was added, over a thirty minute periodat 05, a solution of 2-diethylamino-4,6-dichloro-s-triazine in 75 mls.of dioxane. The mixture was heated at 5560 for 90 minutes, and refluxedfor 30 minutes. A solution of 4.0 g (0.10 mole) of sodium hydroxide wasadded, bringing the pH to a slight pink color with phenolphthalein. Thereaction product was refluxed for 3 hours more and then poured into oneliter of cold water. After standing, the reaction product solidified.This product was filtered, washed with water and then dried. The crudeproduct (13.9 g, 93.3 percent yield) was recrystallized three times frompetroleum ether. The colorless needles obtained had a melting point ofAnalysis for C H N O,

Calcd.: C, 52.32; H. 8.78; N. 28.17 Found C. 52.58; H, 8.88; N. 28.20

EXAMPLE 9 2-(N-n-Propylhydroxyamino)-4,6-bis-(diethylamino)striazine I2,4-Bis-(diethylamino)-6-chloro-s-triazine was prepared by the addition,at 05, of 2 moles of an aqueous solution of diethylamine to anacetone-water slurry containing one mole of cyanuric chloride. Two molesof sodium hydroxide solution was added at 4550- while maintaining thealkalinity slightly below the phenolphthalein end point. The resultingoil was separated, dissolved in ether, extracted with water, dried withanhydrous magnesium sulphate, filtered and concentrated toconstantweight. There was obtained a 94 percent yield of a liquid product.

To a solution of 15.0 g (0.2 mol) of n-propylhydroxylamine in 60 mls. of1:1 dioxane/water was added in 30 minutes at O5, a solution of 25.7 g(0.10 mol) of 2.4-bis-diethylamino-6-chloro-s-triazine in 30 mls. ofdioxane. The mixture was warmed to 55 for minutes and refluxed for 30mintues. The reaction mixture was cooled to 50 and a solution of 4 g(0.1 mol) of sodium hydroxide in 20 mls. of water was added as needed,while maintaining the pH slightly below the red of phenolphthalein.About 24 hours was required for the completion of the reaction period.The reaction mixture was poured into 2 liters of water. The product wasextracted into ether. The ethereal solution was extracted with aqueoushydrochloric acid which was neutralized with aqueous sodium hydroxideliberating the product which was dissolved in ether, washed with water,dried and concentrated at a constant weight. The yield of colorlessliquid product was 20.8 g (70.2 percent yield); n 25 1.5211.

Found EXAMPLE l0 2,4-Bis-(dibutylamino)-6-N-hydroxyamino-s-triazine Aslurry of 1 mole of cyanuric chloride was prepared in acetone/water and2 moles of dibutylamine was added dropwise thereto accompanied bystirring and cooling. An aqueous solution containing 2 moles of sodiumhydroxide was added at a temperature of 4045, the pH being maintained atslightly pink to phenolphthalein. Two liquid phases were obtained. Theupper organic phase was dissolved in ether, washed with water, driedwith anhydrous magnesium sulphate, filtered and concentrated to constantweight. There was obtained in 95 percent yield 2,4-bis (dibutylaminoyb6- chloro-s-triazine.

Free hydroxylamine was prepared, under nitrogen, by the addition, at-atemperature of less than 22, of 1 mole of aqueous sodium hydroxide to1.06 moles of concentrated hydroxylamine hydrochloride solution. To thissolution was added, in a thin stream at a temperature of 26, a solutionof 0.25 moles of the 2,4- bis-(dibutyl-amino)-4-chloro-s-triazine,prepared by the above procedure, in dioxane. The resulting solution washeated at a temperature of 5560, for 1 hour, then at reflux for 3.5hours. The mixture was cooled and the reaction product was then added to1 liter of water. The phases were separated. The upper organic phase wasdissolved in ether, washed with water, dried with anhydrous magnesiumsulphate and concentrated to constant weight under vacuum. The productpartially crystallized on standing. This was followed by slurrying withn-heptane, cooling to l and then the mixture was filtered, while cold.The resulting colorless fine needles exhibited a melting point of 7881,and on.recrystallization from methanol/water, the melting point was79.58l.5.

Analysis for C H N 6O Calc'd.: C, 62.26; H, 10.45; N, 22.93

Found C, 62.10; H, 10.29; N, 23.20

EXAMPLE 1 1 3-(N-Propyl-N-hydroxyamino)propionamide Propyl hydroxylamine(7.5 g, 0.1 mole) was dissolved in mls. of methanol. To this was added,at a temperature of 2530, 7.1 g acrylamide (0.1 mole) in 10 mls. ofmethanol. The reaction was exothermic. The reaction mixture was heatedto 60 and kept at this temperature for 2 hours. The methanol wasevaporated under vacuum and the product was recrystallized from benzene.A yield of 4.9 g of the desired product melting between 101 and 103 wasobtained.

Analysis for C H N O Calcd.: C, 49.29, H, 9.65; N, 19.16 Found C, 49.49;H, 9.75; N, 9.14

EXAMPLE 12 3,8'-Hydroxyimino-bis-propionamide Hydroxylaminehydrochloride (28 g) was dissolved in 250 mls. of methanol. Sodiummethylate (21.6 g, 0.4 mol) in 200 mls. of methanol was added at atemperature of O-5. Sodium chloride precipitated at this point.Acrylamide (57 g, 0.8 mol) in 150 mls. of methanol was added at atemperature of 10. No exothermic reaction could be observed at thispoint. The temperature was allowed to rise slowly and the reaction wasexothermic at around 2025 and reached a maximum of 28. When thetemperature of the reaction mixture dropped to about 20, the sodiumchloride was filtered off and the solution was allowed to stand overnight. Crystallization occurred. The crystals were filtered and thenrecrystallized from methanol and dried. A yield of 35.2- g (50.3 percentyield) was obtained. The melting point was 132.5l33.5 (decomposition).

Analysis for C H N O Calcd; C, 41.13; H, 7.48; N, 23.99

Found C, 41.38; H, 7.26; N, 23.87

EXAMPLE 13 N-Propyl-N-(pchlorobenzyl)-hydroxy1amine.

Propyl hydroxylamine (2.6 g, 0.11 mol) was dissolved in 50 mls. of ethylalcohol. p-Chlorobenzyl chloride (17.7 g, 0.1 1 mol) in 50 mls. of ethylalcohol was added at room temperature. The reaction was noted to beslightly exothermic. Sodium carbonate (5.8 g) in 35 mls. of water wasthen added slowly at 25-30. A precipitate of sodium bicarbonate wasobtained. The mixture was refluxed for 2 hours and it was noted thatmost of the sodium bicarbonate dissolved. At room temperature, themixture was filtered off and the alcohol evaporated leaving a waxy solidresidue in water. This was extracted with ether and washed with water. Afluffy solid crystallized from the ether 1.5 g). The ether solution wasevaporated leaving behind 17.2 of a low melting solid. This material wasdissolved in ether, extracted with dilute hydrochloric acid and theaqueous extract washed with ether. The aqueous solution was neutralizedwith sodium hydroxide, extracted with ether. The ethereal solution waswashed with water, dried and then evaporated. The crude yield of productwas 13.7 g; melting point 48-56. On recrystallization from hexane, ayield of 9.4 g (42.9 percent) was obtained; melting point 6466 Sodium3-(N-n-Propyl-N-hydroxyamino)Propane Sulfonate The reaction of 0.1 moleof n-propyl hydroxylamine with 0.1 mole of propane sultone was allowedto take place in benzene for 3 days at ambient temperature. The benzenewas decanted from a colorless viscous liquid product which wasconcentrated to constant weight under vacuum. The yield of sulfonic acidwas 78 percent; the neutral equivalent was 220 (theory 197). The acidwas converted in aqueous solution to the sodium salt by reaction with anequivalent amount of sodium hydroxide. The aqueous solution wasconcentrated to dryness. The colorless foamy solid was triturated withbenzene, filtered and dried.

Bis-( 3,5 -ditbutyl-4-hydroxybenzyl) Hydroxylamine A solution ofhydroxylamine was prepared under nitrogen by the neutralization of asolution of 28.5 g (0.41 mole) of hydroxylamine hydrochloride in 33 ml.water with 16 g (0.40 mole) of sodium hydroxide in 35 ml water at 20. Tothis solution was added dropwise at 2-6 over 30 minutes a solution of25.5 g (0.10 mole) of 3,5-di-t-butyl-4-hydroxybenzyl chloride in ml ofdioxane. The reaction mixture was heated at 50-55 for 1 hour and atreflux for 1 hour. The reaction product was evaporated under vacuum toremove dioxane and the residue was extracted with ether. The organicphase was washed with water, dried with anhydrous MgSO, and filtered.The ethereal solution was concentrated to dryness. The residue wastriturated with petroleum ether to yield a solid which wasrecrystallized twice from benzene, m.p. l97.

Analysis for C H,;NO

Calc'd.: C. 76.71; H, 10.09; N. 2.98

Found C, 77.49; H, 9.77; N. 2.81

The IR and NMR spectra were in conformance with the structure.

Depending upon the material to be protected and the severity ofoxidation to be encountered, various concentrations of the compounds ofthis invention may be 0.001 percent by weight of one or more of theactive compounds of the present invention to about percent is employed.However, in many instances, concentrations of anti-oxidant well belowthe latter figure give adequate protection. Thus, lubricating oilconcentrations of from 0.01 to 2 percent by weight of the activecompound are usually adequate. Generally it is preferred to use from0.05 to about 3 percent by weight of the additive compound since it isfound that concentrations within this range provide adequateanti-oxidant protection.

, employed as anti-oxidants. Generally, from about i

2. The compound 2,4-bis-(octylthio)-6-(N-hydroxyamino)-s-triazine.